An algae-based polymer material as a pesticide adjuvant for mitigating off-target drift.

Off-target pesticide drift from cropland is a major source of pesticide exposure to pollinating insects inhabiting crop and wildlands in the lower Mississippi Delta (LMD) in the USA. This study is aimed to develop a drift-reducing pesticide adjuvant that is less/nontoxic to honeybees. Ongoing toxicology experiments with two widely-used insecticides and sodium alginate (SA) pointed out reductions in honeybee mortality compared to an industry standard reference polyacrylamide (PAM). When used as an adjuvant to spray the same insecticides described above, SA did not interfere in killing the target pests. Therefore, SA has been tested as a drift-reducing pesticide adjuvant to protect honeybees. Spray experiments in the lab were carried out in four sets: (i) water only, (ii) water and adjuvant, (iii) water and pesticide, and (iv) water, pesticide and adjuvant. Each set contained 18 treatment combinations to cover the ranges in spray pressure (three), adjuvant dose (three), and spray nozzles (two). The droplet spectrum was analyzed using a P15 image analyzer. Diameters of 10 %, 50 % and 90 % volumes (DV10, DV50, and DV90), droplet velocity, standard deviation and relative span were measured. The drift reduction potential (DRP) of SA was analyzed by (i) dose, (ii) spray pressure, and (iii) nozzle type. The DRP of SA is compared to that of PAM. Additionally, three field experiments were carried out to analyze the efficiency of SA in reducing pesticide drift. The results from our experiments collectively indicate that SA has significant potential in mitigating drift as well as minimizing pesticide toxicity to honeybees.

High-throughput analysis of polyethoxylated tallow amine homologs in citrus using a modified QuEChERS-HILIC-MS method.

A new method is described based on ultrahigh-performance liquid chromatography-mass spectrometry (UHPLC) with electrospray mass spectrometry detection for comprehensive quantitative analysis of 66 polyethoxylated tallow amine (POE-tallowamine) homologs in citrus. Efficient separation, reduced band broadening, and high sensitivity were achieved by employing an acetonitrile-aqueous solution containing a 10 mM ammonium formate gradient on a hydrophilic interaction chromatography (HILIC) column with a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method. The quantitative accuracy and precision of the method were improved by the use of matrix-matched calibration standards. At spiked levels of (50 + 250) µg/kg, (200 + 1000) µg/kg, and (500 + 2500) µg/kg POE-5 and POE-15 (1:5), the average recoveries of the POE-tallowamine homologs ranged from 71.9 to 112%, with RSDs < 16.6%. The limits of detection (LODs) and limits of quantification (LOQs) for POE-tallowamine homologs were 0.01-2.57 and 0.03-8.58 µg/kg, respectively. The method was successfully applied to determine POE-tallowamine in citrus samples from typical Chinese regions in 2021. POE-tallowamine was detected in all 54 samples, and the highest concentration (143 µg/kg) of POE-tallowamine was found in Jelly orange from Zhejiang Province, which might indicate a higher usage and demand of glyphosate herbicides in Zhejiang.

Nanocarrier-Loaded Imidaclothiz Promotes Plant Uptake and Decreases Pesticide Residue.

There is a great demand for improving the effective utilization of pesticides and reducing their application for sustainable agriculture, and polymeric nanoparticles have provided strong technical support for the efficient delivery of pesticides. To this context, we tried to construct a relatively safe imidaclothiz nano-delivery system for enhanced plant uptake, reduced pesticide residue and improved bioactivity toward green peach aphids. The imidaclothiz could be assembled with the hydrophobic core of SPc through hydrophobic association, which led to the self-assembly of nanoscale imidaclothiz/SPc complex consisting of nearly spherical particles. The SPc decreased the contact angle of imidaclothiz drops and remarkably increased the plant uptake. Furthermore, the bioactivity and control efficacy of imidaclothiz were significantly improved with the help of SPc in both laboratory and field. Excitingly, the residue of imidaclothiz decreased with the help of SPc 7 d after the treatment due to the faster degradation of nanoscale imidaclothiz/SPc complex, which exhibited no negative effects on agronomic traits of tobacco plants. The current study successfully constructed a nano-delivery system for imidaclothiz, which can not only increase the effective utilization of pesticides, but also decrease the pesticide residue.

Biotoxicity Evaluation of a Cationic Star Polymer on a Predatory Ladybird and Cooperative Pest Control by Polymer-Delivered Pesticides and Ladybird.

Although employing nanocarriers for gene/drug delivery shows great potential in agricultural fields, the biotoxicity of nanocarriers is a major concern for large-scale applications. Herein, we synthesized a cationic star polymer (SPc) as a pesticide nanocarrier/adjuvant to evaluate its safety against a widely used predatory ladybird (Harmonia axyridis). The application of SPc at extremely high concentrations nearly did not influence the hatching of ladybird eggs but it led to the death of ladybird larvae at lethal concentration 50 (LC50) values of 43.96 and 19.85 mg/mL through the soaking and feeding methods, respectively. The oral feeding of SPc downregulated many membrane protein genes and lysosome genes significantly, and the cell membrane and nucleus in gut tissues were remarkably damaged by SPc application, revealing that the lethal mechanism might be SPc-mediated membrane damage. Furthermore, the oral feeding of SPc increased the relative abundance of Serratia bacteria in ladybird guts to result in bacterial infection. Coapplication of ladybird and SPc-loaded thiamethoxam/matrine achieved desired control efficacies of more than 80% against green peach aphids, revealing that the coapplication could overcome the slow-acting property of ladybirds. To our knowledge, this is the first attempt to investigate the polymer-mediated lethal mechanism toward natural enemies and explore the possibility of coapplying SPc-loaded pesticides and natural enemies for pest management.

Simple, Effective, and Ecofriendly Strategy to Inhibit Droplet Bouncing on Hydrophobic Weed Leaves.

Despite small-molecule surfactants and polymers being widely used as pesticide adjuvants to inhibit droplet bouncing and splashing, they still have intrinsic drawbacks either in the easy wind drift and evaporation, the unfavorable wettability, or the usage of nonrenewable resources. In this paper, we found that upon droplet impacting, 1D nanofibers assembled from natural glycyrrhizic acid (GL) could pin on the rough hydrophobic surface and delay the retraction rate of droplets effectively. Using GL as a tank-mixed adjuvant, the efficiency of glyphosate to control the weed growth was improved significantly in the field experiment, which addressed the dilemmas of current adjuvants elegantly. Our work not only provides a constructive way to overcome droplet bouncing but also prompted us to verify in future if all 1D nanofibers assembled from different small molecules can display similar control efficiencies.

Rapid analysis of tristyrylphenol ethoxylates in cucumber-field system using supercritical fluid chromatography-tandem mass spectrometry.

Tristyrylphenol ethoxylates (TSPxEOs), nonionic surfactant adjuvants, are widely used to replace alkylphenols in many agricultural formulations. Herein, a rapid and sensitive method based on a modified quick, easy, cheap, effective, rugged, and safe "QuEChERS" and supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS) method was developed to quantify TSPxEOs in cucumber, leaves, and soil. Following optimization, the tested oligomers were fully separated within 8 min. The matrix-matched calibration standards showed satisfactory linearity with coefficients of determination (R2) ≥ 0.991. The limits of quantification (LOQs: 0.001-0.048 µg kg-1) were excellent for TSPxEOs (x = 6-29). The average recoveries at three (low, medium, and high) fortification levels were ranged between 62.5% and 112.9% with relative standard deviations (RSDs) ≤20.0% for TSPxEOs (x = 6-29) in various matrices. The method was successfully applied to determine TSPxEOs residual levels in field-incurred samples. Conclusively, the developed method is versatile and could be used for monitoring TSPxEOs in food and environmental samples.

Simultaneous determination of three pesticide adjuvant residues in plant-derived agro-products using liquid chromatography-tandem mass spectrometry.

Herein, an accurate and reliable isotope-labelled internal standard method was developed and validated for simultaneous determination of three polar pesticide adjuvants, namely 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone in plant-derived agro-products. Matrices, including apple, cabbage, tomato, cucumber, rice, and wheat were extracted with a modified quick, easy, cheap, effective, rugged, and safe "QuEChERS" method and purified with a new clean-up sorbent (Z-Sep). A hydrophilic interaction liquid chromatography column (HILIC), exhibiting a lipophilic-hydrophilic character, was used to separate the three analytes over 10min using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Matrix effects in various matrices were evaluated and an isotope-labelled internal standard method was employed to compensate for ion enhancement/suppression effects. At three fortification levels (2.0, 5.0, and 20.0µg/kg), the mean recoveries ranged from 78.5 to 112.1% with relative standard deviations (RSDs)<11.0% for all tested analytes. The limits of detection (LODs) and quantification (LOQs) were 0.04-0.45 and 0.12-1.58µg/kg in various matrices, respectively. The developed experimental protocol was successfully applied to monitor different samples purchased from local markets in Beijing, China. In conclusion, the developed method exhibited both high sensitivity and satisfactory accuracy and is suitable for the simultaneous determination of the three tested pesticide adjuvant residues in agro-products of plant origin.